Nitrourea-urea-aldehyde condensation products



PatentedNov.18,1941 2,263,239

UNITED. STATESTIVPATENT OFFICE NITROUREA-URE'AY-ALDEHYDE CONDENSATION PRODUCTS I came F. DAlelio and-Joe B. Holmes, Pittsfield;

Mass., assignors to General Elect -'c Company, a corporation of New. York No Drawing. Application August 9,1939,

Serial No. 289,281 4 14 Claims. (01. 260-68) This invention relates to new condensation ureas, also may be'used in carrying the present products and to methods of making the same. invention into effect. Such salts may be formed The invention is concerned more particularly by treating an aldehyde-reactable nitrated urea with self-curing aminoplasts, by which is meant with a basic substance. The basic substance heat-convertible resinous condensation products 5 may be of an organic or inorganic nature. EX- prepared from amino or amido compounds and amples of basic substances which may be used having the inherent characteristic of curing unin making salts of nitrated ureas are ammonia, der heat or under heat and pressure to the inpotassium hydroxide, calcium hydroxide, methyl soluble, infusible state without the addition of a amine, trimethyl amine, ethanol amine, ethylene curing accelerator'or catalyst. diamine, triethanol amine, etc. A more specific In the production of aminoplasts it has hereexample. of a salt of an aldehyde-reactable nitofore been common practice in converting such trated urea is the sodium salt of nitrourea, which materials to the insoluble, infusible state to inmay be produced by treating nitrourea with a corporate into the condensation product or into solution of sodium-hydroxide, thus: the molding composition a latent or an active 0 (direct) curing catalyst. As pointed-out more particularly hereafter, this technique and the NHflONHNO2+N30H NHCONN\ final products have not been wholly satisfactory. 0N8

We have discovered that self-curing amino- The term t t -m t urea") plasts can b pro uced by C densing a nonas used generally hereafter is intended to include a d e an a ph ti a y r example within its meaning nitrated ureas, salts of niformaldehyde, and a nitrated urea, specifically H t a and mixtures th f,

nitrourea. The initial condensation may be car- I producing th n w condensation products, ried out at normal or at elevated temperatures, h h, may b d rib d more specifically as coin e presence or absence of a condensation 2.5 condensation products, the choice of the aliphatic catalyst and under alkaline, neutral or acid conaldehyde m nent i dependent; largely upon ditions. g economic considerations and upon the particular The non-mtrated e Component m y b for properties desired in thefinished product. We

instance, urea (NH2CONH2) se thiourea; prefer to use as the aldehydic component foriminou'rea (guanidine); aldehyde-reactable submaldehyde or compounds en'gendering formaldestituted ureas, thioureas and iminoureas such as hyde such as paraformaldehyde hexamethylenemethyl urea, ecetyl urea, behZOyl urea, P e y tetramine, etc. For some applications we may e e asymmetrical diethyl urea, yl Urea; use, for instance, acetaldehyde, propionaldehyde, h y u ethyliden urea, ethylol butyraldehyde, 'acrolein, methacrolein, crotonalu m y e urea, dicyandiamide y dehyde, etc., mixtures thereof, or mixtures of h o fl a u y h e ua formaldehyde (orcompounds engendering fordme, .fimi o ll e, ea fi (guahidine maldehyde) with such aliphatic aldehydes. In t y y e) and guanoline (guanido carbonic general the longer the chain ofthe aliphatic aldeethyl e The h hell-nitrated hyde, the slower the cure of the resinous conas used.generally herein and m the appended densation product and the softer is the final claims, has reference to and means an aldehydeproduct,

eacta e o e ureaillumelousfixamples In the heat-convertible resinous condensation f which a been g v n a 7 products of this invention the self-curing prop- The nitrated ureas used in practicing this inerty of the product is. imparted thereto by creatvention are those having at least one hydrogen ing a resin molecule having this inherent chara'c atom attached to a nitrogen'atom in the urea teristic. This is a discovery of great practical grouping. As a result, :they are aldehyde. reactsignificance. It makes possible the production of able and for purpose of'brevi'ty are so termed molding compositions of uniform curing charachereafter. An example of an aldehyde-re'actable teristics, which compositions yield molded artinitrated urea is nitrourea, NI-l'zCONHNOz These cles free from imperfections's'uch as blisters, disnitratedureas are not to be confused with urea colorations, etc. Such imperfections are due ,nitratesfwhich are salts. An. example of such usually to localized curing that often occurs in asaltis urea nitrate, NHzCONH-HNOa resinous material of the admixed-catalyst type. Salts of aldehyde-reactable nitrated ureas, As the value of the molded article, especially alone or mixed with aIdehyde reactabIe nitrated light-colored articles, is materially influenced by I any means for decreasing or eliminating entirely the production of imperfect articles which must be scrapped or sold at reduced price is of considerable commercial importance.

. As a result of our invention the difllculties attendant the production of molding compositions comprising aminoplasts oi the admixed-catalyst type are avoided. With such compositions there was, despite the most careiul precautions, considerable variation in the curing rates 01 the individual batches. This made diillcult the maintenance of production schedules. Considerable variation also was common even among different portions 01' the same batch of material, as evidenced by the appearance oi the cured article.

The resin syrups and molding compositions of this invention may be stored for long periods of time without material alteration. In marked contrast therewith the prior heat-convertible aminoplasts, more particularly those containing direct or active curing catalysts such as acids, for example hydrochloric, ethyl suliuric, phthalic,

chloroacetic, phosphoric, etc., lacked time or storage stability. This necessitated early use of the material after incorporating the catalyst.

Further, the molding compositions oi this invention cure rapidly under heat or under heat and pressure and have good plastic flow during molding. Hence molded articles of even the most complicated designs can be produced rapidly and economically. The cured products have good light stability, excellent water resistanceuand surface finish and, in general, meet the strength, hardness and other requirements of the particular service application.

In carrying the present invention into efiect the condensation reaction between the aliphatic aldehyde and the other components preferably is started under neutral or alkaline conditions. Neutral conditions may be established by neutralizing (it necessary) either the mixed components or the individual component or components prior to admixture. Any substance yielding an alkaline aqueous solution may be used in obtaining alkaline conditions for the initial condensation reaction. In some cases it maybe desirable, in order more quickly to initiate reaction between the starting materials, to add a small amount of a suitable organic or inorganic acid. Thereafter the solution is treated to eliminate acidic conditions due to acid or acid salts. That is, the mass is neutralized or is made alkaline by adding an alkaline substance. The reaction is then caused to proceed further to produce the self-curing aminoplasts of this invention.

In obtaining the neutral, alkaline or acid con ditions above described we may use, for example, ammonia, sodium hydroxide or carbonate, cal cium hydroxide, methyl amine, diethyl amine, tri-isopropyl amine, ethanol amines, tri-isopropanol amine, etc., mixtures of such alkaline substances, inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic, acrylic, crotonic, malonic, etc., or acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc., or mixtures of acids, of acid salts, or of acids and acid salts. Sodium hydroxide and carbonate and calcium hydroxide are examples of fixed alkalies (alkaline substances).

Various ways may be employed for efiecting initial reaction between the components. For example, we may first mix all thereactants and effect condensation between the mixed reactants in the presence or absence of addition agents, as for instance, condensation catalysts, fillers, plasticizers, other natural or synthetic resinous bodies, solvents or diluents, etc. Alternatively, we may add the nitrated urea to a partial condensation product of a non-nitrated urea and an aliphatic aldehyde and efiect further condensation between the components. Or, we may first condense the nitrated urea with aliphatic aldehyde, add the resulting product to a non-nitrated urea-allphatic aldehyde partial condensation product and then cause the reaction to proceed further. Or, we may condense or partially condense the nitrated urea with a mol excess of an aliphatic aldehyde, add a non-nitrated urea to this condensation product and efiect further reaction between the components. Still other ways may be employed in combining the components and in producing the unmodified or modified condensationproducts of this invention, as will be readily understood by those skilled in the art as the description oi the invention proceeds.

In practicing this invention we may use a nitrated urea with a single non-nitrated urea and a single aldehyde in producing the self-curing aminoplasts. It was also surprisingly found that a salt oi a nitrated urea, specifically alkali-metal salts of a nitrated urea, e. g., sodium nitrourea and potassium nitrourea, could be used with a nitrated urea, e. g., nitrourea, in carrying the present invention into effect. The rate oi cure of resinous bodies produced in this way may be controlled by varying the ratio of the nitrated urea to the nitrated urea salt. This discovery has a great practical value in the manufacture of this particular self-curing aminoplast. By its application we may use a large ratio of nitrated urea. to nitrated urea salt and obtain stable, yet fast curing resins. By decreasing the ratio of nitrated urea to nitrated urea salt, we are able to produce, under identical conditions as before,

resins which are more readily controlled and oi a slower cure. These condensation reactions may proceed under a wide variety of time, temperature and pressure conditions. The temperature of reaction may vary from room temperature to the reflux temperature of the reactants at reduced, atmospheric or superatmospheric pressures.

The products obtained as described above properly may be designated as intermediate condensation products. They are heat-convertible resinous bodies which alone or mixed with fillers, pigments, dyes, lubricants, plasticizers, etc., may be used, for example, as molding compositions. The modified or unmodified resinous masses are selfconvertible under heat or under heat and pressure to the insoluble iniusible state.

Depending upon the particular reactants employed and the particular conditions of reaction, these intermediate condensation products vary from-clear, colorless, syrupy, water-soluble liquids to viscous, milky dispersions and gel-like masses of decreased solubility in ordinary solvents, such as alcohol, glycol, glycerine, water, etc. These liquid intermediate condensation products may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentration. The liquid compositions may be used, for instance, as surface coating materials, in' the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, as anti-creasing agents, in producing laminated articles, and for numerous other'purposes. The

Example 1 Parts by weight Urea 24.0 Nitrourea. 0.018 Aqueous formaldehyde (pH=7) (37.1%

approximately) 65.0 Alpha flock 24.0 Water 40.0

The above components were mixed and refluxed for 30 minutes. To the resulting mass was added 0.17 part zinc stearate and the compound dried at 50 C. Under heat and pressure this molding composition produced molded articles that were well cured and had good color. The compound could be dyed to obtain molded articles of delicate shades which are of especial commercial value.

Example 2 Parts by weight Urea 60.0 Aqueous ammonia (28%) 7.6

Aqueous formaldehyde (37.1% approximately (approx. 60 part HCHO) 161.0 Sodium hydroxide (in 15 parts of water) 0.04 Nitrourea 0.5

The above components with \the exceptitin f the nitrourea were mixed and refluxed 20 o 30 minutes after which the above stated a ount of nitrourea was added to the syrup. The s rup was not refluxed further. Sixty-one (61) arts alpha flock and 0.4 part zine stearate were aided to form a molding composition. The compo nd was heated to effect further condensation simultaneously with drying. Molded articles for ed from this compound possessed good color, ere well cured, and had excellent water resistance.

Example 3 Parts-by weight Urea 60.0 Aqueous ammonia (28%) l 7.6

Aqueous formaldehyde -(37.1% approxii mately) 61.0 Sodium hydroxide (in 15 parts of Water) 0.06 Nitrourea 1.0 Sodium nitrourea 2.25

All of the components except the nitrourea and sodium nitrourea were mixed and solution was effected by stirring. The nitrourea and sodium nitrourea in water solution were next added. The mass was heated under reflux for minutes. The syrup was allowed to cool to r'oom temperature. It was quite fluid and formed a good curing resin 0n the hot plate at 150 C. The syrup was mixed with'70 parts alpha flock and 0.4 part zinc stearate to form a molding composition. The compound was dried at 50 C. This compound when molded under heat and pressure gave excellent molded articles. The compound had good flow, and the molded articles had exceptional I translucency.

Example 4 Same formulation as Example 3 but 1.5 parts sodium nitrourea were used. The components were mixed exactly as before and heated under curing characteristics toreflux for exactly the same time. The syrup produced in this case formed a faster curing resin on the hot plate at 150 C. than did the'syrup in Example 3. Asthe syrup cooled it became thicker and finally a gel formed. This gel was dried at C. and molded under heat and pressure to form clear molded articles.

Example 5 Parts by weight Urea 60.0 Aqueous ammonia (28%)-n. 7.6

Aqueous formaldehyde (37.1% approximately) 161.0 Sodium hydroxide 0.04 Nitrourea 0.6

Example 6 Parts by weight Urea 36.0 Nitrourea 0.036 Aqueous formaldehyde (37.1% approximately) L l 121.0

The above components were mixed\ and heated under reflux for 30 minutes. The resulting syrup yielded a fast curing resin on the hot plate at C. It was used for preparing molding compounds.

Condensation products of urea and formaldehydealone, prepared as described under Examples 1 to 6, inclusive, but not inter-condensed with the specific nitrated urea mentionedfin the individual example are heat-non-convertible. In 1 other words, they will not cure under heat or 1 under heat and pressure to the insoluble infusible state. i

In certain cases, it.- may be advantageous to,'

use a. single nit ated urea with a plurality of\ non-nitrated ureas. Thus, to modify the char-1 acteristics of thelmolded product we may use a mixture of, for example, urea and dicyandh, amide, with a single nitrated urea. i The ratio of the reactants to each other may be considerably varied but, in general, it is desirable to use at least one mol of an aliphatic aldei hyde for each mol of mixed (total) non-nitrated urea and nitrated ureaf. In producingthe heatconve tible resinous condensation products of this invention, the proportion of nitrated urea in all cases is at least sufilcient to irripart selfthe resin. Ordinarily not exceeding substantially mol nitrated urea is used for each mol iof non-nitratedlurea. No. advantage accrues -'fr 111 using an amount of nitrated urea abov'e th curfe the desired curing rate. Further, the use of high amounts of nitrated urea is undesirable for most molditng applications because of the greater difiiculty in obtaining molded articles of suitable flovv and hardness, but may not be objectionable f0. material. f

From the foregoing it will befiseen that the particular mol ratio of nitrated urea to the other components is dependent somewhat upon the inherent characteristics of the nitrated urea and the curing characteristics and other properties desired in the heat-convertible and heat-hardened resinous condensation products. Thus, in

minimum required to seother applications of the producing these new condensation products we may cause to react ingredients comprising es- "sentially the following components: (1) a nonnitrated urea, (2) an aliphatic aldehyde and (3) a small molar amount not exceeding substantially one-fourth mol of an aldehyde-reactable N-nitrated urea or a salt thereof or a mixture of an aldehyde-reactable N-nitrated urea and a salt (3). For example, we may produce a heatcurable (or heat-cured) resinous composition comprising a soluble, fusible (or insoluble, infusible) condensation product of ingredients comprising essentially the following components in the stated molar ratios: (1) one mol of a nonnitrated urea (specifically the organic compound corresponding to the formula NHzCONHz) (2) at least one mol (e. g., from 1 to 2 mols) of an aliphatic aldehyde, for instance formaldehyde, and (3) a small molar amount not exceeding substantially one-fourth mol of nitrourea or a salt thereof or a mixture of nitrourea and a salt thereof. For molding applications the ratio of the aliphatic aldehyde to urea substance may be considerably varied, but generally will be within the range of 1 to 2 mols aliphatic aldehyde for each mol of urea substance. No particular advantage ordinarily accrues from the use of higher amounts of aldehyde Approximately 2 mols aliphatic aldehyde per mol urea substance usually gives very satisfactory results, particularly from the viewpoint of optimum yields of condensation product per unit cost.

The fundamental resins of this invention may be varied widely by introducing other modifying bodies before, during or after effecting condensation between the primary components Thus, as modifying agents we may use, for example, monohydric alcohols such as ethyl, propyl, isopropyl,- butyl, amyl, etc. alcohols; polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerine pentaerythritol, trimethylol nitro methane, etc.; monoamides such as formamide, acetamide, stearamide, acrylic acid amides (acryloamides), benzamide, toluene sulfonamide, etc.; polyamides such as adipic diamide, phthalamide and the like; amines such as ethylene diamine, aniline, phenylene diamine, amino phenols, em.

The modifying bodies also may take the form of high molecular weight bodies with or without resinous characteristics, for example partially hydrolyzed wood products, lignin, proteins, protein-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, aniline-aldehyde condensation products, modified or unmodified, saturated orv unsaturated polybasic acid-polyhydric alcohol condensation products, sulfonamide-aldehyde resins, water-soluble cellulose derivatives, natural gums and resins such as copal,,shellac, rosin, etc; polyvinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl acetals, speciflcally polyvinyl formal, synthetic linear condensation products such as the superpolyamides, etc.

Other modifying agents of a plasticizing or softening nature also may be incorporated with the, condensation products of this invention.

. Examples of such modifying agents are the phthalate esters, for instance dimethyl phthalate, diethyl phthalate, dibutyl phthalatejetc the phosphate esters such as tricresyl phosphate',

triphenyl phosphates, etc.

Dyes, pigments and opacifiers (e, g., barium sulfate, zinc sulfide, titanium compounds such as the oxides, flaked aluminum, copper and the like) may be incorporated into the compositions to alter the visual appearance and the optical properties of the finished product. Mold lubricants such as the metallic soaps of the high molecular weight fatty acids, for example the stearates and palmitates of tin, zinc, etc., waxes such as carnauba, high melting point paraffin waxes, etc., may be added to facilitate molding of the compositions. Various fillers may be used to provide a wide variety of molding compositions. The choice of the filler depends upon the particular application for which the molded article is to be used. As fillers may beused, for instance, bleached or unbleached wood flour, alpha cellulose in flock form, sheets or cuttings of paper, cloth, canvas, etc., asbestos in powdered or long or short fiber length, powdered or flaked mica, wood chips, short or long wood fibers, syn thetic or natural continuous threaded fibers, glass fibers in continuous filament or fabric (woven or felted) form, etc.

In the preparation of molding compositions from the resinous bodies of this invention, the non-dehydrated or the partially dehydrated resins may be compounded with the above addition agents in accordance with procedures well known to those skilled in the plastics art. The wet composition may be dried in the usual manner either at normal (room) temperature or at elevated temperatures in a preheated stream of air or under the influence of reflected heat energy. The dried compound may be densifled through the usual processes of working in a Banbury mixer, or by rolling, pelleting or other means, followed by grinding and screening to the desired particle size. These molding compositions may be molded at elevated temperatures, preferably between 100 and 150 C., and at suitable pressures. The molding pressures generally range between about 1000 and about 4000 pounds per square inch, more particularly from about 2000 to 3000 pounds per square inch.

In addition to their use in molding compositions, -the condensation products of this invenv tion are especially suitable for use as fire retardants, water repellents and sizings when applied to wood or the like, or to fibrous materials such as silk, cotton, 'wool, synthetic organic .fibers, etc., in continuous filament, thread, fabric both coated and impregnated by any suitable means, for example by spraying with, or immersing in, a solution of the treating agent and thereafter removing the solvent.

The modified or unmodified products of this invention have a wide variety of other uses, for instance in making buttons, clock cases. radio cabinets, dishes and other household utensils,.

decorative novelties and various other cast, molded and laminated articles of manufacture. They may be used in making arc-extinguishing tubes capable of evolving an arc-extinguishing gas under the heat of the arc, in the production of wire or baking enamels, and for bonding or cementing together'mica flakes to form a laminated mica article. They also may be used in making laminated fibrous sheetmaterials wherein superposed layers ofcloth, paper, etc., are

devices, and for other purposes.

,What we claim as new and desireto secure by Letters Patent of the United States is:

.1. A composition of matter comprising the heiafihardenable condensation product of ingr'edients comprising essentially the following components: (1) a non-nitrated urea, (2) an aliphatic aldehyde and (3) a small molar amount not exceeding substantialy one-fourth mol of a nitrogenous compound selected from the class consisting of nitrourea, salts of nitrourea and mixtures of nitrourea and salts thereof, said aliphatic aldehyde being present in the molar ratio of at least one mol aliphatic aldehyde for each mol of the sum of the non-nitrated urea of (1) plus the nitrogenous compound of (3).

2. A composition of matter comprising an alcohol-modified] heat-hardenable condensation product of ingredients comprising essentially the following components: (2) an aliphatic aldehyde and (3) a small molar amount not exceeding substantially one-fourth mol of nitrourea, said aliphatic aldehyde being present in the ratio of at least one mol aliphatic aldehyde for each mol of the sum of the 'nonnitrated urea of (1) plus the nitgiourea of (3).

3. A heat-curable resinous'condensation prodnot of ingredients comprising essentially the following components: (1) a non-nitrated urea, (2) formaldehyde and (3) a small molar amount not exceeding substantially one-fourth mol of nitrourea, said formaldehyde being present in the molar ratio of at least one mol formaldehyde for each mol of the sum of the non-nitrated urea of (1) plus the nitrourea of (3).

4. A heat-curable resinous composition comprising a soluble, fusible condensation product of ingredients comprising essentially the following components in the stated molar ratios: (1) 1 mol of urea, (2) from 1 to 2 'mols of formaldehyde and (3) a small amount not exceeding substantialy M mol of nitrourea.

5. A product comprising the cured resinous condensation product of claim 3.

6. A condensation product of ingredients comprising essentially the following components: (1) a non-nitrated urea, (2) an aliphatic alde hyde and (3) a small molar amount not exceeding substantially one-fourth mol of a salt of nitrourea, said aliphaticaldehyde being present in the molar ratio of at least one mol aliphatic aldehyde for each mol of the sum of the nonnitrated urea of (1) plus the nitrourea salt of (3).

(1) a non-nitrated urea,

tially the followingcomponents in the stated molar ratios: 1) 1 mol urea, (2) -at least 1 mol formaldehyde and (3) a small amount not exceeding substantially A mol ofa salt of nitrourea.

9. A heat-hardenable resinous composition comprising a soluble, fusible resinous condensation product of ingredients comprising essentially. the following components in the stated molar ratios: (1) -1 mol urea,-.-(2,) at least 1 mol formaldehyde and (3) a small amount notexceedingsub stantially mol of a -mixture of nitrourea and a salt ofnitrourea.

10. The method of producing a heat-hardenable resinous composition which comprises reacting to resin formation ingredients comprising essentially the followingcomponents in the stated molar ratios: (1) l niol of a non-nitratedv urea, (2) at least 1 mol of an aliphatic aldehyde and (3) a small amount 'not exceeding substantially 4 mol of a nitrogenous compound selected from the class consisting of nitrourea, salts of nitrourea and mixtures of nitrourea and salts thereof.

11. A composition comprising the product of reaction of (1) the partial condensation product obtained by reaction, while admixed with an alkaline substance comprising ammonia, of urea and formaldehyde in the ratio of one mol of the former to from one and one-half to two and one-half mols of the latter and (2) nitrourea in a small molar amount not exceeding substantiallyone-fourth mol for each mol of the urea component of (1).

12. 'A composition comprising the product of reaction of (1) the partial condensation product obtained by reaction, in the presence of alkaline substances comprising ammonia and sodium hydroxide, of urea and formaldehyde in the ratio of one mol of the former to from one and onehalf to two and one-half mols of the latter and resulting partial condensation product a nitrog- '7. A heat-hardenable resinous composition comprising the heat-convertible reaction product of (1) the partial condensation product obtained by reaction, under alkaline conditions, of

enous compound selected from the class consisting of nitrourea, salts of nitrourea and mixtures of nitrourea and salts thereof in a small molar amount not exceeding substantially one-fourth mol for each mol of the urea component of the said urea-formaldehyde partial condensation product, and causing the said nitrogenous compound to intercondens'e with thesaid partial condensation product.

14. The method which comprises effecting partial reaction, under alkaline conditions due to the presence between both ammonia and sodium hydroxide, of urea and formaldehyde in the ratio of one mol of the former to from one and one-half to two and one-half mols of the latter, adding to the resulting .partial condensation product nitrourea in a small molarramount not exceeding substantially one-fourth mol for each mol of the urea component of the said ureaformaldehyde partial condensation product, and causing the said nitrourea to intercondense with the said partial condensation product.

GAETANO F. DALELIO.

.. I JOE B. HOLMES.

CERTIFICATE OF CORRECTION.

. Patent No. 2,265,289. November 18, 19).;1.

GAETANO F. D'ALELiO, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows; Page 5, first 6 1 m, iine 17, clainl for "substant ialy" read --substantially--; and second column, line 63'; claim 11.1., for '"betwee'n" read --of--; line 61;, claim 11 for "of" read --between-; and. that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of January, A. D. 19!;2,

Henry Van Arsdale (Seal) Acting Conhnissioner of Patents. 

